EP0197408A2 - Verfahren zur Herstellung von omega-Lactamen, insbesondere Caprolactam - Google Patents

Verfahren zur Herstellung von omega-Lactamen, insbesondere Caprolactam Download PDF

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Publication number
EP0197408A2
EP0197408A2 EP86103982A EP86103982A EP0197408A2 EP 0197408 A2 EP0197408 A2 EP 0197408A2 EP 86103982 A EP86103982 A EP 86103982A EP 86103982 A EP86103982 A EP 86103982A EP 0197408 A2 EP0197408 A2 EP 0197408A2
Authority
EP
European Patent Office
Prior art keywords
reaction
acid
range
cycloaliphatic
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP86103982A
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English (en)
French (fr)
Other versions
EP0197408A3 (de
Inventor
Paolo Senni
Leandro Zuliani
Sergio Ferruzzi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chimica Del Friuli SpA
Original Assignee
Chimica Del Friuli SpA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chimica Del Friuli SpA filed Critical Chimica Del Friuli SpA
Publication of EP0197408A2 publication Critical patent/EP0197408A2/de
Publication of EP0197408A3 publication Critical patent/EP0197408A3/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
    • C07D201/02—Preparation of lactams
    • C07D201/08—Preparation of lactams from carboxylic acids or derivatives thereof, e.g. hydroxy carboxylic acids, lactones or nitriles

Definitions

  • This invention relates to a method of preparing m-lactams, in particular caprolactam, with improved yield and purity.
  • caprolactam can be prepared by reacting cycloaliphatic compounds with a nitrosating agent in the presence of a dehydrating agent.
  • US Patent 3,356,675 and Italian Patent Application 27018 A/79 disclose preparing caprolactams from cycloaliphatic compounds, including hexahydrobenzoic acid, by reacting them with nitrosyl acid sulphate in concentrated sulphuric acid or oleum, and utilizing oleum as the dehydrating agent.
  • Italian Patent Application 27018 A/79 claims a process for preparing ⁇ -lactams containing 5 to 14 carbons in a multi-stage reactor, implemented by racting a cycloaliphatic acid having the general formula where n varies from 3 to 13, and/or the corresponding anhydrides, with a nitrosating agent in the presence of a dehydrating agent.
  • Hexahydrobenzoic acid also referred to as cyclohexanecarboxylic acid, being preferred.
  • any of the agents specified in US Patent 3,356,675 may be used.
  • Nitrosyl sulphuric acid is preferred for the production of caprolactam.
  • dehydrating agents are: SO" chlorosulphonic acid, anhydride of chlorosulphonic acid, phosphoric anhydride, or even the very anhydride of hexahydrobenzoic acid, in which case, in calculating the molar ratios, one mole anhydride of hexahydrobenzoic acid is the equivalent of one mole SO,; thus, for simplicity, reference will be made hereinafter to SO, -equivalent moles, to specify either one mole SO, or one mole of some other anhydride serving the same anhydrifying function.
  • the reaction temperature can vary in the range of 30° to 100°C, and in particular where hexahydrobenzoic acid is used, the reaction temperature would be preferably in the 60° to 90°C range.
  • the reaction may be conducted in either discontinuous, semicontinuous, or continuous stirred reactors.
  • a continuous multi-stage reactor would be preferred with hexahydrobenzoic acid, anyhow.
  • Thermal regulation of the reaction may be effected by using, in the reaction system, a particular inert thermostating solvent which can remove reaction heat by absorption as evaporation heat, thereby .constancy of the. reaction temperature is achieved by boiling the thermostating solvent.
  • thermostating solvents are: cyclohexane, n-eptane, n-hexane, n-pentane, chlorinated or fluorinated hydrocarbons, nitrocom- pounds, etc.
  • control parameters of this reaction are:
  • a further object of this invention is to arrange for decreased production of the strongly acidic byproducts (i) which form the outstanding proportion of all the byproducts formed.
  • the molar ratio of dehydrating agent to nitrosating agent is preferably within the range of 0.7 to 1.1.
  • the small amount of water which is added during the second reaction step is such that a by-weight concentration of SO 3 equivalents is obtained which ranges from 2% to 10% of the reaction mass. That amount is preferably within the range of 5% to 6% where hexahydrobenzoic acid is used as the cycloaliphatic acid.
  • the dehydrating agent is preferably oleum at a concentration in the 36% to 50% range, preferably in the 38% to 40% range where hexahydrobenzoic acid is used as the cycloaliphatic acid. These concentration levels are significantly higher than the oleum concentration employed with prior methods - (30% to 37%).
  • the molar ratio U would be preferably in the 0.4 to 0.6 range; the temperature of the first and second reaction steps is preferably in the 60° to 80°C range.
  • the small amount water which is added during the second reaction step may be in the form of an acqueous solution containing sulphuric acid and possibly ⁇ -lactams.
  • the method of this invention is preferably conducted on a continuous basis through a plurality of consecutive stages which implement said first and second reaction steps.
  • said plural consecutive stages would be split in two serially arranged discrete reactors.
  • the first of the reactors receives the nitrosating agent and completes the markedly exothermic part of the lactamization reaction. No nitrosating agent is preferably added through the last stages of the first reactor.
  • the second of the reactors receives the small amount water and completes the low-exothermic part of the reaction.
  • the unreacted cycloaliphatic acid reclaiming step is carried out by hydrolysis with water of the product from the second reactor, that hydrolysis process being conducted at a temperature preferably in the 20° to 30°C range.
  • the hydrolyzed product is separated into an acqueous phase containing M -iactams and an organic phase containing the unreacted cycloaliphatic acid and the thermostating solvent.
  • Examples 1-6 have been conducted as semicontinuous tests (with only the nitrosylsulphuric acid solution being fed continuously) on the system shown in Figure 1.
  • the method steps are:
  • this invention allows the S02 concentration to be increased during the first reaction step; this results in decreased byproducts (iv), and decreased concentration of SO 3 in the second reaction step, which affords decreased byproducts (i). As may be taken from the Tables, to that decrease in byproducts there corresponds an increased caprolactam yield.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)
  • Pyrrole Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP86103982A 1985-03-27 1986-03-22 Verfahren zur Herstellung von omega-Lactamen, insbesondere Caprolactam Withdrawn EP0197408A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT2008985 1985-03-27
IT20089/85A IT1187655B (it) 1985-03-27 1985-03-27 Procedimento per la preparazione di w-lattami,in particolare caprolattame

Publications (2)

Publication Number Publication Date
EP0197408A2 true EP0197408A2 (de) 1986-10-15
EP0197408A3 EP0197408A3 (de) 1990-03-14

Family

ID=11163709

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86103982A Withdrawn EP0197408A3 (de) 1985-03-27 1986-03-22 Verfahren zur Herstellung von omega-Lactamen, insbesondere Caprolactam

Country Status (9)

Country Link
US (1) US4647661A (de)
EP (1) EP0197408A3 (de)
AR (1) AR241134A1 (de)
BR (1) BR8601349A (de)
ES (1) ES8705859A1 (de)
IN (1) IN167050B (de)
IT (1) IT1187655B (de)
MX (1) MX165249B (de)
SU (1) SU1588278A3 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4793994A (en) * 1986-06-27 1988-12-27 Gaf Corporation Compositions used in permanent structure altering of hair
US4775527A (en) * 1986-06-27 1988-10-04 Gaf Corporation Compositions used in permanent alteration of hair color
US5153307A (en) * 1991-07-31 1992-10-06 International Business Machines Corporation Stabilization of polyamide alkyl ester solutions
US5284357A (en) * 1991-11-01 1994-02-08 Tinkler Michael R Apparatus and method for damping deflections and vibrations in skis
CN100374418C (zh) * 2006-03-01 2008-03-12 湘潭大学 一种合成己内酰胺及其低聚物的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT255397B (de) * 1963-03-06 1967-07-10 Inventa Ag Verfahren zur Herstellung von ω-Lactamen
DE1620263A1 (de) * 1964-05-15 1970-03-19 Snia Viscosa Societa Naz Ind A Verfahren zur Herstellung von Caprolaktam aus Cyclohexylverbindungen
GB2061927A (en) * 1979-11-02 1981-05-20 Snia Viscosa Process for the preparation of w-lactams

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3022291A (en) * 1962-02-20 cuhno
US4349437A (en) * 1980-07-24 1982-09-14 Rickett David A Automatic and continuous chemical feed system

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT255397B (de) * 1963-03-06 1967-07-10 Inventa Ag Verfahren zur Herstellung von ω-Lactamen
DE1620263A1 (de) * 1964-05-15 1970-03-19 Snia Viscosa Societa Naz Ind A Verfahren zur Herstellung von Caprolaktam aus Cyclohexylverbindungen
GB2061927A (en) * 1979-11-02 1981-05-20 Snia Viscosa Process for the preparation of w-lactams

Also Published As

Publication number Publication date
IT8520089A0 (it) 1985-03-27
US4647661A (en) 1987-03-03
ES553304A0 (es) 1987-05-16
ES8705859A1 (es) 1987-05-16
AR241134A2 (es) 1991-11-29
IN167050B (de) 1990-08-25
MX165249B (es) 1992-11-04
EP0197408A3 (de) 1990-03-14
IT1187655B (it) 1987-12-23
BR8601349A (pt) 1986-12-02
AR241134A1 (es) 1991-11-29
SU1588278A3 (ru) 1990-08-23

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